Biodegradable sulfate detergents

ABSTRACT

Biodegradable sulfate detergents may be prepared by condensing butadiene with allyl alcohol to form a hydroxymethylcyclohexene, thereafter ring alkylating said compound with a 1-alkene in the presence of a free-radical generating compound and hydrogen chloride to form an n-alkyl-substituted hydroxymethylcyclohexene, sulfating and neutralizing the compound to form the desired product.

United States Patent [1 1 Bloch 1 Sept. 23, 1975 BIODEGRADABLE SULFATEDETERGENTS 75 Inventor: Herman s. Bloch, Skokie, in.

[73] Assignee: Universal Oil Products Company, Des Plaines, Ill.

[22] Filed: Nov. 4, 1974 211 App]. No.: 520,695

Related U.S. Application Data [63] Continuation-impart of Ser. No.277,836, Aug. 3,

1972, Pat. No. 3,867,421.

[52] U.S. Cl 260/457; 260/617 R; 260/631 R;

252/545; 252/547 [51] Int. Cl. C07C 141/12 [58] Field of Search.....260/457, 458, 617 R, 631 R [56] References Cited UNITED STATES PATENTS2,435,403 2/1948 Morris et al. 260/617 R 2,863,925 12/1958 Starchu260/617R 3,385,873 5/l968 Caldwell 3,392,185 7/1968 Walts et al 260/457Primary Exar'r'linerBernard Helfin Assistant Examiner-Nicky ChanAttorney, Agent, or Firm.lames R. Hoatson, Jr.; Raymond H. Nelson;William H. Page, ll

[5 7] ABSTRACT 8 Claims, No Drawings BIODEGRADABLE SULFATE DETERGENTSCROSS-REFERENCE TO RELATED APPLICATIONS This application is acontinuation-in-part of my copending applieationSer. No. 277,836 filedAugust 3, 1972, now U.S. Pat. No. 3,867,421,.all the teachings of whichare specifically incorporated herein by reference.

This invention relates to a process for preparing biodegradabledetergents. More specifically, the invention is concerned with a novelprocess comprising a series of steps hereinafter set forth in greaterdetail whereby alkali metal, alkaline earth metal or ammonium salts ofan n-substituted eyclohexenyl methano sulfate are formed, said compoundsbeing biodegradable in nature.

One of the major problems which is prevalent in population centersthroughout the world is the disposal of sewage containing detergentsdissolved therein. Such disposal problems are especially trying in thecase of branch-chained alkylaryl detergents. These detergents producestable foams in hard or soft waters in such large quantities that thefoam clogs sewage treatment facilities, and destroys the bacteria whichare necessary for proper sewage treatment. In many rivers, streams,lakes, etc., which act as a water supply for the aforesaid populationcenters, there are found these unwanted foams and suds. As hereinbeforeset forth, the presence of these unwanted foams or suds is due in manyinstances to the use of detergents which are nonbiodegradable in natureand which will not break down by bacterial action thereon. Thenon-biodegradable nature of these detergents is due to the fact that thealkyl side chain of the molecule is in many instances highly branchedand therefore not readily attacked by the organisms which wouldordinarily destroy the molecule. In contradistinetion to this, the useof straight chain alkyl substituents on the ring will permit thedetergents to be destroyed and therefore foams or sudswill not build upon the surface of the water.

It is therefore an object of this invention to provide a novel methodfor the production of detergents which show biodegradability in bothurban and rural sewage disposal systems.

In one aspect an embodiment of this invention resides in a process forthe preparation of a biodegradable detergent which comprises the stepsof: (a) condensing butadiene with allyl alcohol in a Diels-Alderreaction at a temperature in the range of from about 50 to about 190 C.and a pressure of from atmospheric to about 100 atmospheres to formhydroxymethylcyclohexene; (b) ring alkylating saidhydroxymethyleyclohexene with a l-alkene in the presence of an organicperoxy free-radical generating compound and hydrogen chloride at atemperature at least as high as the decomposition temperature of saidfree-radical generating compound to form an n-alkyl-substitutedhydroxymethyleyclohexene; (c) sulfating said n -alkyl-- substitutedhydroxymethylcyclohexene with a sulfating agent selected from the groupconsisting of sulfuric acid, oleum, sulfur trioxide, and chlorosulfonicacid at a temperature of from about to about 60 C. to form the sulfateester thereof; (d) neutralizing said ester with a neutralizing agentselected from the group consisting of alkali metal base, alkaline earthmetal base, ammonia, ammonium hydroxide, lower alkyland alkanol amineand benzyl amine to form the resultant biodegradable detergent, and (e)recovering the same.

A specific embodiment of this invention is found in a process for thepreparation of a biodegradable detergent which comprises the steps ofcondensing butadiene with allyl alcohol at a temperature in the range offrom about to about 190 C. and a pressure in the range of from aboutatmospheric to about 100 atmospheres, ring alkylating the resultanthydroxymethylcyclohexene with l-octene in the presence of di-t-butylperoxide and hydrogen chloride at a temperature at least as high as thedecomposition temperature of said di-t-butyl peroxide, sulfating theresultant n-octyl hydroxymethyleyclohexene with sulfuric acid at atemperature in the range of from about 0 to about C., neutralizing thesulfate ester with sodium hydroxide at a temperature in the range offrom about ambient to about 40 C. and recoveringthe resultantsodium(noetyl-3-eyclohexenyl )methano sulfate.

Other objects and embodiments will be found in the following furtherdetailed description of the present invention.

As hereinbefore set forth, the present invention is concerned with aprocess for the preparation of detergents which are biodegradable innature, the process being effected in a series of steps. In the firststep of the reaction, butadiene is condensed with allyl alcohol in aDiels-Alder type condensation to give 4-hydroxymethylcyclohexene. TheDiels-Alder condensation is effeeted at elevated temperatures, usuallyin the range of from about 50 to about 190 C. and at a pressure rangingfrom atmopsheric to about atmospheres. The reaction pressure may beafforded by the autogenous pressure of the butadiene or by a combinationof butadiene and a substantially inert gas such as nitrogen or argon,the amount of pressure which is utilized being that which is sufficientto maintain at least a portion of the reactants in the liquid phase.

The 4-hydroxymethylcyelohexene which has been prepared according to theabove paragraph is recovered and selectively alkylated utilizing anolefinic hydrocarbon as the alkylating agent. The selective alkylationin which the alkyl substituent is positioned on the ring rather than onthe side chain is effected by treating the reactants in the presence ofa free-radical generating compound and hydrogen chloride. In thepreferred embodiment of the invention, the olefinic hydrocarbon which isutilized as the alkylating agent will comprise a l-alkene containingfrom 3 to about 20 carbon atoms in length and preferably from about 4 toabout 14 carbon atoms. By utilizing the l-alkene and an alkylationcatalyst comprising a free-radical generating compound and a promotorcomprising hydrogen chloride, it is possible to obtain a normal alkylside chain on the cyclohexene ringrather than a secondary alkyl sidechain which would result if the alkylation were effected in the presenceof an acidic catalyst of the Friedel Crafts type or sulfuric acid, etc.Specific examples of the alpha-olefinic hydrocarbons which are utilizedas alkylating agents include propene, lbutene, lpentene, l-hexene,l-heptene, l-octene, l-nonene, l-

decene, l-undecene, l-dodecene, l-tridecene, ltetradecene, Lpentadecene,l-hexadeeene, lheptadecene, loctadecene, l-nonadecene, l-

eicosene, etc.

The catalysts which are used in this step of the invention will includeperoxy compounds, containing the bivalent radical OO- which decompose toform free radicals which initiate the general reaction and are capableof inducing the condensation of the hydroxymethylcyclohexene with thel-alkene. Examples of these catalysts include the persulfates,perborates, perearbonates of ammonium and of the alkali metals, ororganic peroxy compounds. The organic peroxy compounds constitute apreferred class of catalysts for use in the invention and includeperacetic acid, persuccinic acid, methyl ethyl ketone peroxide, methylisobutyl ketone peroxide, acety] peroxide, dipropionyl peroxide,di-t-butyl peroxide, butyryl peroxide, lauroyl peroxide, benzoylperoxide, tetralin peroxide, urea peroxide, t-butyl perbenzoate, t-butylhydroperoxide, methylcyclohexyl hydroperoxide, cumene hydroperoxide,diisopropylbenzene hydroperoxide, etc. Mixtures of peroxy compoundcatalysts may be employed or the peroxy compoundcatalyst may be utilizedin admixture with various diluents. Thus, organic peroxy compounds whichare compounded commercially with various diluents which may be usedinclude benzoyl peroxide compounded with calcium sulfate, benzoylperoxide compounded with camphor, phthalate esters, etc. Only catalyticamounts (less than stoichiometric amounts) need be used in the process.

The alkylation of the hydroxymethylcyclohexene with the l-alkene iseffected at elevated reaction temperatures which should be at least ashigh the initial decomposition temperature of the free-radicalgenerating catalyst, such as the peroxide compound, in order to liberateand form free radicals which promote the reaction. In selecting aparticular reaction temperature for use in the process of the presentinvention, two considerations must be taken into account. Firstsufficient energy by means of heat must be supplied to the reaction sothat the reactants, namely, the hydroxymethylcyclohexene and thel-alkenes, will be activated sufficiently for condensation to take placewhen free radicalsare generated by the catalyst. Second, free-radicalgenerating catalysts such as peroxy compounds. particularly organicperoxides, decompose at a measurable rate with time in a logarithmicfunction dependent upon temperature. This rate of decomposition can beand ordinarily is expressed as the half life ofa peroxide take place,and these radicals must be formed at a temperature at which thereactants are in a suitably activated state for condensation. When thehalf life of the free-radical generating catalyst is greater than 10hours, radicals are not generated at a sufficient rate to cause thereaction of the process of the present inven-. tion to go forward at apractically useful rate. Thus the reaction temperature may be within therange of from about to about 300 C. and at least as high as thedecomposition temperature of the catalyst, by which is meant atemperature such that the half life of the freeradical generatingcatalyst is not greater than 10 hours. Since the half life for eachfree-radical generating catalyst is different at different temperatures,the exact temperature to be utilized in a particular reaction will vary.However, persons skilled in the art are well acquainted with the halflife vs. temperature data for different free-radical generatingcatalysts. Thus it is within the skill of one familiar with the art toselect the particular temperature needed for any particular catalyst.However, the operating temperatures generally do not exceed thedecomposition temperature of the catalyst by more than about C. sincefree-radical generating catalysts decompose rapidly under suchconditions. For example, when a free-radical generating catalyst such ast-butyl perbenzoate is used, having a 50% decomposition temperature (in10 hours) of approximately C., the operating temperature of the processis from about 105 C. to about 205 C. When di-tbutyl peroxide having a 10hour,'50% decomposition temperature of about C. is used, the process isrun at a temperature ranging from about 125 to about 225 C. Higherreaction temperatures may be employed, but little advantage is gained ifthe temperature is more than the hereinbefore mentioned 100 C. higherthan the 10 hour, 50% decomposition temperature of the catalyst. Thegeneral effect of increasing the operating temperature is to acceleratethe rate of condensation reaction of the hydroxymethylcyclohexene withthe lalkene. However, the increased rate of reaction is accompanied bycertain amounts of decomposition. In addition to the elevatedtemperatures which are utilized, the reaction may also be effected atelevated pressures ranging from I to about 100 atmospheres or more, thepreferred operating pressure of the process being that which is requiredto maintain a substantial portion of the reactants in liquid phase.Pressure is not an important variable in the process of this invention.However, because of the low boiling points of some of the reactants, itis necessary to utilize pressurewithstanding equipment to insure liquidphase conditions. In batch type operations, it is often desirable toutilize pressure-withstanding equipment to charge the reactants and thecatalyst to the vessel and to pressure the vessel with 10 or 30 or 50 ormore atmospheres of an inert gas such as nitrogen. This helps to insurethe presence of liquid phase conditions. However, when the mole quantityof reactants is sufficient, the pressure which they themselves generateat the temperature utilized is sufficient to maintain the desired phaseconditions.

Furthermore, the concentration of the catalyst employed in this processmay vary over a rather wide range but it is desirable to utilize lowconcentrations of catalysts such as from about 0.1% to about l07c'of thetotal weight of the combined starting materials charged to the process.The reaction time may be within the range of from less than one minuteto several hours, depending upon temperature and half life of thecatalyst. Generally speaking, contact times of at least 10 minutespreferred.

In addition to the free-radical generating catalyst, the alkylation isalso effected in the presence of a hydrogen chloride'compound. Thehydrogen chloride compound is used as a'promoter for the reaction andalso is used to prevent or inhibit telomerization, said telomerizationbeing a polymerization reaction in which unwanted side reaction productsmay be formed. The hydrogen chloride may'be present as anhydroushydrogen chloride, as concentrated hydrochloric acid or as a more diluteaqueous solution of hydrochloric acid, the hydroehloric acid beingpresent in an amount of from 5% to about 38% in said aqueous solution.

The resulting compound comprising n-alkyl substitutedhydroxymethylcyclohexenes is then subjected to the sulfating step inwhich the sulfate ester of the methylcyclohexene is prepared. Thissulfating step is accomplished by treating the alkyl-substitutedhydroxymethylcyclohexene with a conventional sulfating agent such assulfuric acid, oleum, sulfur trioxide, chlorosulfonic acid, etc., attemperatures ranging from about 0 to about 60 C., the particulartemperature which is to be employed being dependent upon the type ofsulfating agent which is used. For example, when the sulfating agentcomprises sulfur trioxide or oleum, the reaction may be effected at atemperature in the subambient range, that is, from about 0 up to about25 C. When employing other sulfating agents such as sulfuric acid, thereaction may be effected over the entire range hereinbefore set forth,that is, from about 0 up to about 60 C. Likewise the use ofchlorosulfonic acid as the sulfating agent will permit the reaction tobe effected at ambient (about to C.) temperatures.

The sulfate ester which is thus prepared is then neutralized byutilizing a conventional neutralizing agent such as an alkali metalbase, an alkaline earth base, ammonia or an amine. Specific examples ofthese neutralizing agents will include sodium hydroxide, potassiumhydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide,magnesium hydroxide, calcium hydroxide, strontium hydroxide, ammonia,ammonium hydroxide, amines such as ethanol amine, propanol amine, benzylamine, N,N-dimethylbenzyl amine, N,N- diethylbenzyl amine, dimethylamine, diethyl amine, dipropyl amine, etc. The preferred neutralizingagents comprise ammonium hydroxide, sodium hydroxide or potassiumhydroxide due to the greater availability and relatively lower cost ofthese compounds. The neutralization reaction, being exothermic innature, is usually run under a controlled temperature system, thepreferred temperature for the reaction being from about ambient up toabout 40 C. The control of the temperature is usually effected byutilizing cooling means including ice, cooling coils, etc., whereby thealkali metal, alkaline earth metal or ammonium salt of the sulfate isobtained.

The process of this invention in which biodegradable sulfate detergentsare prepared may be effected in either a batch or continuous operation.When a batch type operation is used, a quantity of the allyl alcohol isplaced in an appropriate apparatus such as an autoclave of the rotatingor mixing type. The autoclave is sealed and the butadiene is chargedthereto or in an alternate method, a mixture of butadiene and an inertgas such as nitrogen is charged thereto, until the desired operatingpressure is reached. The autoclave is thereafter heated to the desiredoperating temperature within the range hereinbefore set forth andmaintained thereat for a predetermined residence time which may rangefrom 0.5 up to about 10 hours or more in duration. Upon completion ofthe desired residence time, heating is discontinued, the autoclave isallowed to return to room temperature, the excess pressure is vented andthe reaction mixture is recovered therefrom. Thehydroxymethylcyclohexene is separated from any unreacted allyl alcoholby conventional means such as distillation or by any other separationmeans known in the art and placed in a second reaction vessel along witha free-radical generating compound and the l-alkene which is to beutilized as the alkylating agent. This second reaction vessel may be aflask provided with condensing means or an autoclave of the rotating ormixing type. In addition, a promoter comprising hydrogen chloride eitherin gaseous form as hydrogen chloride or in aqueous form as hydrochloricacid is added to the reactor which is thereafter heated to the desiredoperating temperature which, as hereinbefore set forth, is at least ashigh as the decomposition temperature of said freeradical generatingcompound. After maintaining the alkylation reaction at this temperaturefor a predetermined period of time which may range from about 0.5 up toabout 10 hours, heating is discontinued, the reaction mixture is allowedto return to room temperature and the n-alkyl-substitutedhydroxymethylcyclohexene is separated and recovered by conventionalmeans.

The n-alkyl hydroxymethylcyclohexene is then treated with a sulfatingagent to form the sulfate ester thereof. This treatment is accomplishedby placing the cyclohexene in an appropriate apparatus and addingthereto the sulfating agent. This apparatus may comprise a reactionflask if the sulfating agent is in liquid form or a pressure vessel ifsulfur trioxidc is utilized as the sulfating agent. The sulfatingreaction is effected at a temperature ranging from about 0 to about 60C., the reactor being cooled or heated according to the particularsulfating agent which is employed, said cooling or heating means whichwill be employed being of the conventional type such as cooling coils,ice, etc., or heating coils, etc., if elevated temperatures areemployed.

The resultant sulfate ester may be separated from unreacted startingmaterial after recovery from the reaction vessel, but the reaction ispreferably carried virtually to completion so that the product may thenbe neu tralized by treatment with a compound of the type hereinbeforeset forth. To accomplish this, the sulfate ester may be introduced intoan appropriate apparatus also provided with cooling means in order tocontrol the temperature of the reaction which is exothermic in nature.The neutralizing agent such as the alkali metal base, alkaline earthmetal base, ammonia or amine is usually present in the reactor in aslight molar excess over the sulfate ester and the latter is graduallyadded with adequate mixing of the reactants. The reaction is allowed toproceed while controlling the temperature, said residence time alsobeing in a range of from 0.5 up to about 10 hours or more in duration.Upon completion of the desired residence time, the reaction mixture isrecovered and subjected to conventional means of separation whichinclude washing, drying, extraction, etc., whereby the desired alkalimetal, alkaline earth metal or ammonia salts of the n-alkyl-substitutedcyelohexenemethano sulfates are recovered.

It is also contemplated within the scope of this invention that thedesired product may be prepared while employing a continuous manner ofoperation. When the continuous manner of operation is to be used, thestarting materials comprising the allyl alcohol and butadiene arecontinuously charged to a reactor which is maintained at the properoperating conditions of temperature and pressure. After passage throughthis reactor for a predetermined period of time, the effluent iscontinuously withdrawn and subjected to a separation step whereby theunreacted allyl alcohol and butadiene are separated from thehydroxymethylcyclohexene and recycled to form a portion of the feedstock while the latter .is continuously charged to an alkylationapparaously charged to the apparatus through separate lines or, if sodesired, one or more of the reactants may be admixed with another priorto entry into said reactor and the resulting mixture charged thereto ina single stream. After completion of the desired residence time in thealkylation apparatus, the reactor effluent is continuously withdrawn,again subjected to separation steps whereby unreacted startingmaterials, promoter and by-products are separated from thealkylsubstituted hydroxymethylcyclohexene. The unreacted startingmaterials are recycled to the apparatus to form a portion of the feedstock while the n-alkyl-substituted hydroxymethylcyclohexene iscontinuously charged to the sulfating reactor. In this reactor theaforementioned cyclohexene is subjected to the action of a sulfatingagent which is also continuously charged. to this reactor, said reactorbeing maintained at the proper operating conditions, especiallytemperature. After passage through this reactor for a predeterminedperiod of time, the effluent is continuously withdrawn, again subjectedto separation steps, if necessary, whereby the unreacted-substitutedcyclohexene and sulfating agent are separated from the sulfate ester andrecycled to form a portion of the feed stock in this reactor, thesulfate ester being continuously charged to the neutralization zone. Inthis zone, the sulfate ester is subjected to the action of theneutralizing agent which is also continuously charged thereto. Inasmuchas the reaction is exothermie innature, as hereinbefore set forth, thetemperature of the last named reactor is carefully main- .tained in arange of from about C. up to about 40 Czin order that any unwanted sidereactions are minimized and ahigher yield of the desired product isobtained thereby. As in the prior steps in this continuous type ofoperation, the reactor effluent is also continuously withdrawn and thefinal product is separated and recovered while any unreacted startingmaterials are recycled to'the neutralization zone to form a portion of Ithe feed stock-thereto. I The following examples are given to illustratethe process of the present invention which, however, are" not intendedto limit the generally broadscope of the present invention in strictaccordance therewith.

EXAMPLE 1 mixture is subjected to fractional distillation whereby the-desired product comprising 4-hydroxyrnethylcyclohexene is separatedfrom any unreacted allyl alcohol and recovered.

The 4-hydroxymethylcyclohexene which is recovered is then placed in theglass liner of a rotating autoclave along with l-octene, the chargestock usually consisting of a molar excess of thehydroxymethylcyclohexene over the l-octene in a range of from about1.5:1 to about 2:1 moles of hydroxymethylcyclohexene per mole ofl-octene.-ln addition, 7 grams of di-t-butyl peroxide and 20 grams ofconcentrated hydrochloric acid are also placed in the autoclave. Theautoclave is sealed and nitrogen is pressed in until an initialoperating pressure of 30 atmospheres is reached. The autoclave andcontents thereof are then heated to a temperature of C.'and maintainedin a range of from about 130 to about 140 C. for a period 3f 8 hours. Atthe end of this 8-hour period, heating is discontinued, the autoclave isallowed to return to room temperature and the excess pressure isdischarged therefrom. The autoclave is then opened, the reaction mixtureis recovered and subjected to fractional distillation, usually underreduced pressure, whereby the desired product comprising then-octyl-substituted 4-hydroxymethylcyclohexene is recovered. Then-octyl-substituted hydroxymethylcyclohexene is then placed in areaction vessel and a slight excess of sulfuric acid is added thereto.The reaction apparatus is warmed to a temperature of 30 C. andmaintained thereat for a period of about 4 hours. At the end of thistime,.heating is discontinued and the reactor is allowed to return toroomtemperature. The resulting sulfate ester is then placed in anotherreaction vessel provided with cooling means and an aqueous solution ofsodium hydroxide in a slight excess is slowly added to the sulfateester, the temperature of the reaction being maintained at about 25 C.

by means of cooling coils. At the end of a 2-hour period, the reactionmixture is dried and the desired prodln this example 1 mole proportionof allyl alcohol is placed in the glass liner of a rotating autoclavewhich is thereafter sealed into the autoclave. A mole proportion ofbutadiene along with a sufficient amount of nitrogen is pressed into theautoclave until an initial operating pressure of 30 atmospheres isreached. The autoclave and contents thereof are then heated to atemperature of 140 C. and maintained in a range of from .to C. foraperiod of 4 hours. At the end of the 4- hour period, heating isdiscontinued. the autoclave is allowed to return to room temperature andthe excess pressure is discharged therefrom. The autoclave is opened andthe reaction mixture is recovered and subjected to fractionaldistillation under reduced pressure whereby the desired productcomprising 4-hydroxymethylcyclohexene is separated and recovered.

The hydroxymethylcyclohexene which is prepared according to the aboveparagraph is then placed in another liner of a rotating autoclave alongwith ltetradecene, the hydroxymethylcyelohexene being present in a molarexcess over the tetradecene. In addition, a catalyst comprising 7 gramsof di-t-butyl peroxide and a promoter comprising 20 grams ofhydrochloric acid are also added to the liner. The liner is then sealedinto the autoclave and nitrogen is pressed in until an initial operatingpressure of 30 atmospheres is reached. The autoclave and contentsthereof are then heated to a temperature of 130 C. and maintained in arange of from 130 to 140 C. for a period of.8 hours. At the end of the8-hou r period,;heating is discontinued, the autoclave is allowed toreturn to room temperature, the excess pressure is discharged and theautoclave is opened. After subjecting the reaction mixture to fractionaldistillation under reduced pressure, the desiredn-tetra-decyl-substituted 4-hydroxymethylcyclohexene is recovered.

As in Example I, the disubstituted cyclohexene is sulfated in a similarmanner with sulfuric acid and neutralized withv an aqueous solution ofsodium. hydroxide whereby the desired product comprising'sodium(ntetradecyl-3-cyclohexenyl)methano sulfate is recovered.;, i i ii EXAMPLEIII In this example 4-hydroxymethylcyclohexene is prepared in amanner similar to that hereinbefore setforth. The thus preparedhydroxymethylcyclohexene islalkylated by reaction with l-decene in asimilar manner to that set forth in the above examples, that is, bytreating a molar-excess of the hydroxymethylcyclohexene with l-decene inthe presence of a catalyst comprising di-tbutyl peroxide and apromotercomprising hydrochloric acid at a temperature of about 130 Ci for aperiod of 8 hours under an initial operating pressure of 30 atmospheresof nitrogen. t

'After. recovery of c the n-decyl-substituted 4-hydroxymethylcyclohexeneby conventional means of separation, the compound is then placed inanother reaction apparatus for preparation of the sulfate ester. In thisstep liquid sulfur trioxide is vaporized and ad mixed with air so thatthe stream which is introduced into the reactor will containapproximately 7 volume 7c of sulfur trioxide. This stream is charged tothe reactor at a temperature of about 10 C. (maintained by coolingcoils) in a sufficient amount so that there is a slight excess of sulfurtrioxide present, said amount being in a range of from about 1 .01 up toabout 1.1 moles of sulfur trioxide per mole of decyl-substitutedhydroxymethylcyclohexene. Upon completion of the addition of the sulfurtrioxide, the resulting mixture is passed to an aging tank and allowedto age for a period of about minutes at ambient temperature to insurecomplete reaction. The sulfate ester is then placed in another reactionapparatus which contains cooling means for regulating the temperature ofthe reaction. An aqueous solution of potassium hydroxide is slowly addedto the sulfate ester during a period of about 30 minutes whilemaintaining the temperature in a range of from about to about C., saidpotassium hydroxide being in a slight molar excess over the sulfateester. At the end of the addition, the mixture is thoroughly stirred fora period of 1 hour and thereafter subjected to conventional means ofdrying and separation whereby the desired biodegradable detergentcomprising potassium(ndecyl-3-cyclohexenyl)methano sulfate is recovered.

EXAMPLE IV In a manner similar to that set forth in the above examples,1 mole proportion of allyl alcohol is placed in the glass liner of arotating autoclave which is thereafter sealed into the autoclave and amole proportion of butadiene along with a sufficient amount of nitrogenis pressed into the autoclave until an initial operating pressure ofatmospheres is reached. Following this, the autoclave and contentsthereof are then heated to a temperature of :140 C. and maintainedthereat for a period of 4 hours, at-the end of which time'heating isdiscontinued, the autoclave is allowed to return to room temperature and.the excess pressure is discharged therefrom The autoclave is opened andthe reaction mixture is treated in a conventional manner to separate andrecover the desired 4-hydroxymethylcyclohexerie.

The thus prepared 4-'hydroxymethylcyclohexene is placed in anotherliner'of arotating autoclave along with l-dodecene,'thehydroxymethylcyclohexene being present in a molar excess over thedodecene. In addition; a catalyst comprising 7 grams of benzoyl peroxideand a promoter comprising 20 g'ramsof hydrochloric acid are also addedtothe liner. The liner is then sealed into the autoclave and nitrogen ispressed in until an initial operating pressure of 30 atmospheresisreached. The autoclave and contents thereof are then heated to atemperature of C. and'maintained in a range of from to C. for a periodof 8 hours. At the end of the 8- hour period. heating is discontinued,the autoclave is allowed to return to room temperature, theexcesspressure is discharged and the autoclave is opened. The reactionmixture is recovered therefrom and subjected to fractional distillationunder reduced pressure whereby the desired n-dodecyl-substitutedhydroxymethylcyclohexene is recovered. i The n-dodecyl-substitutcdhydroxymethylcyclohexene is then placed in areaction vessel and a slightexcess of oleum is added thereto. After warming the reaction apparatusto a temperature of about 30 C. and maintaining said apparatus thereatfor a period of 4 hours, the heating is discontinued and the reactor isal- I lowed to return to room temperature. The thus prepared sulfateester is placed in another reactor which is provided with externalcooling means and an aqueous solution of ammonium hydroxide in a slightexcess is slowly added to the sulfate ester, the temperature of thereaction being maintained at about 20 C. At the end of the slowaddition, the reaction mixture is stirred for an additional period of lhour and the desired product comprising cyclohexenyhmethano sulfate isrecovered therefrom.

EXAMPLE V In like manner 4-hydroxymethylcyclohexene is prepared byreacting equimolar proportions of allyl alco' hol and butadiene in anautoclave under an applied pressure of 30 atmospheres of nitrogen and ata temperature of C. for a period of 4 hours.

The hydroxymethylcyclohexene is recovered and reacted with l-tridecenein the presence of a catalyst comprising dit-butyl peroxide and apromoter comprising hydrogen chloride, this reaction being effected inan autoclave at a temperature in the range of from 130 to C. and apressure of 30 atmospheres for a period of 8 hours.

The resulting n-tridecyl hydroxymethylcyclohexene which is preparedaccording to the above paragraph is then sulfated by treatment withchlorosulfonic acid in a manner similar to that set forth in the aboveexamples and neutralized by treatment with an aqueous solution ofpotassium hydroxide whereby the desired product comprisingpotassium(n-tridecyl-3- cyclohexenyl)methano sulfate is recovered.

I claim as my invention:

l. A process for the preparation of a biodegradable detergent whichcomprises the steps of: v

a. condensing butadiene with allyl alcohol in a Dicls- Alder reaction ata temperature in the range of from about 50 to about 190 C. and apressure of from atmospheric to about 100 atmospheres to formhydroxymethylcyclohexene;

ring alkylating said hydroxymethylcyclohexene with a l-alkenc in thepresence of an organic peroxy freeradical generating compound andhydrogen chloride at a temperature at least as high'as the decompositiontemperature of said free-radical generating compound to form ann-alkylsubstituted hydroxymethylcyclohexene; c. sulfating saidn-alkyl-substituted hydroxymethylcy clohexene with a sulfating agentselected from the group consisting of sulfuric acid, oleum, sulfur trioxide, and chlorosulfonic acid at a temperature of from about 0 to about60 C. to form the sulfate ester thereof;

d, neutralizing said ester with a neutralizing agent se lected from thegroup consisting of alkali metal base, alkaline earth metal base,ammonia, ammonium hydroxide, lower alkyland alkanol amine and benzylamine to form the resultant biodegradable detergent; and

e. recovering the same.

2. The process as set forth in claim 1 in which said sulfating agent ispresent in an amount of from about l.()l to about 1.] moles of sulfatingagent per mole of 12 n-alkyl-substituted hydroxymethylcyclohexene.

3. The process as set forth in claim 1 in which said 1- alkene containsfrom 3 to about 20 carbon atoms.

4. The process as set forth in claim 1 in which said alkene is l-octene,said sulfating agent is sulfuric acid, said neutralizing agent is sodiumhydroxide and said biodegradable detergent is sodium( n-octyl-3-cyclohexenyl)methano sulfate. I

S. The process as set forth in claim 1 in which said alkene is l-decene,said sulfating agent is sulfur trioxide, said neutralizing agent ispotassium hydroxide and said biodegradable detergent ispotassiurn(n-decyl-3- cyclohexenyl)methano sulfate.

6. The process as set forth in claim 1 in which said alkene isl-dodeeene, said sulfating agent is oleum, said neutralizing agent isammonium hydroxide and said biodegradable detergent is ammonium(n-dodecyl-3- cyclohexenyl)methano sulfate. v

7. The process as set forth in claim 1 in which said alkene isl-tridecene, said sulfating agent is-chlorosulfonic acid, saidneutralizing agent is potassium hydroxide and said biodegradabledetergent is potassium(ntridecyl-3-cyclohexenyl)methano sulfate.

8. The process as set forth in claim 1 in which said alkene isl-tetradecene, said sulfating agent is sulfuric acid, said neutralizingagent is sodium hydroxide and said biodegradable detergent issodium(n-tetradecyl-3- cyclohcxenyl )methano sulfate.

1. A PROCESS FOR THE PREPARATION OF A BIODEGRADABLE DETERGENT WHICHCOMPRISES THE STEPS OF: A. CONDENSING BUTADIENE WITH ALKYL ALCOHOL IN ADIELS-ALDER REACTION AT A TEMPERATURE IN THE RANGE OF FROM ABOUT 50* TOABOUT 190*C. AND A PRESSURE OF FROM ATMOSPHERIC TO ABOUT 100 ATMOSPHERESTO FROM HYDROXYMETHYLCYCLOHEXENE, B. RING ALKYLATING SAIDHYDROXYMETHYLCYCLOHEXENE WITH A 1-ALKENE IN THE PRESENCE OF AN ORGANICPEROXY FREE-RADICAL GENERATING COMPOUND AND HYDROGEN CHLORIDE AT ATEMPERATURE AT LEAST AS HIGH AS THE DECOMPOSITION TEMPERATURE OF SAIDFREE-RADICAL GENERATING COMPOUND TO FORM AN N-ALKYLSUBSTITUTEDHYDROHEXYMETHYCYCLOHEXENE, C. SULFATING SAID N-ALKYL SUBSTITUTEDHYDROXYMETHYLCYCLOHEXENE WITH A SULFATING AGENT SELECTED FROM THE GROUPCONSISTING OF SULFURIC ACID, OLEUM, SULFUR, TRIOXIDE, AND CHLOROSULFONICACID AT A TEMPERATURE OF FROM ABOUT 0* TO ABOUT 60* C. TO FORM THESULFATE ESTER THEREOF, D. NEUTRALIZING SAID ESTER WITH A NEUTRALIZINGAGENT SELECTED FROM THE GROUP CONSISTING OF ALKALI METAL BASE, ALKALINEEARTH METAL BASE, AMMONIA, AMMONIUM HYDROXIDE, LOWER ALKYL- AND ALKANOLAMINE AND BENZYL AMINE TO FROM THE RESULTANT BIODEGRADABLE DETERGENT,AND E. RECOVERING THE SAME.
 2. The process as set forth in claim 1 inwhich said sulfating agent is present in an amount of from about 1.01 toabout 1.1 moles of sulfating agent per mole of n-alkyl-substitutedhydroxymethylcyclohexene.
 3. The process as set forth in claim 1 inwhich said 1-alkene contains from 3 to about 20 carbon atoms.
 4. Theprocess as set forth in claim 1 in which said alkene is 1-octene, saidsulfating agent is sulfuric acid, said neutralizing agent is sodiumhydroxide and said biodegradable detergent issodium(n-octyl-3-cyclohexenyl)methano sulfate.
 5. The process as setforth in claim 1 in which said alkene is 1-decene, said sulfating agentis sulfur trioxide, said neutralizing agent is potassium hydroxide andsaid biodegradable detergent is potassium(n-decyl-3-cyclohexenyl)methanosulfate.
 6. The process as set forth in claim 1 in which said alkene is1-dodecene, said sulfating agent is oleum, said neutralizing agent isammonium hydroxide and said biodegradable detergent isammonium(n-dodecyl-3-cyclohexenyl)methano sulfate.
 7. The process as setforth in claim 1 in which said alkene is 1-tridecene, said sulfatingagent is chlorosulfonic acid, said neutralizing agent is potassiumhydroxide and said biodegradable detergent ispotassium(n-tridecyl-3-cyclohexenyl)methano sulfate.
 8. The process asset forth in claim 1 in which said alkene is 1-tetradecene, saidsulfating agent is sulfuric acid, said neutralizing agent is sodiumhydroxide and said biodegradable detergent issodium(n-tetradecyl-3-cyclohexenyl)methano sulfate.